EP1249467B1 - Self-cleaning surfaces due to hydrophobic structure and process for the preparation thereof - Google Patents
Self-cleaning surfaces due to hydrophobic structure and process for the preparation thereof Download PDFInfo
- Publication number
- EP1249467B1 EP1249467B1 EP02004728A EP02004728A EP1249467B1 EP 1249467 B1 EP1249467 B1 EP 1249467B1 EP 02004728 A EP02004728 A EP 02004728A EP 02004728 A EP02004728 A EP 02004728A EP 1249467 B1 EP1249467 B1 EP 1249467B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- particles
- self
- elevations
- fixative
- cleaning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
- C09D181/06—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
- B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
- B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
- B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
- B08B17/065—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
- C08J5/128—Adhesives without diluent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
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Definitions
- the present invention relates to self-cleaning surfaces and methods for their production.
- Articles having extremely difficult to wet surfaces have a number of economically important features.
- the economically most important feature is the self-cleaning effect of difficult-to-wet surfaces, since the cleaning of surfaces is time consuming and costly.
- Self-cleaning surfaces are therefore of the highest economic interest.
- Adhesive mechanisms are usually conditioned by interfacial energy parameters between the two contacting surfaces. As a rule, the systems try to lower their free surface energy. If the free interfacial energies between two components are inherently very low, it can generally be assumed that the adhesion between these two components is weak. Important here is the relative lowering of the free surface energy. For pairings with high and low interfacial energy, the possibilities of interactions are very often important.
- hydrophobic materials such as perfluorinated polymers
- hydrophobic surfaces are known.
- a further development of these surfaces is to structure the surfaces in the ⁇ m range to the nm range.
- U.S. Patent 5,599,489 discloses a method in which a surface can be rendered particularly resistant by bombardment with particles of a corresponding size and subsequent perfluorination.
- Another method is described by H. Saito et al., Service Coatings International 4, 1997, p. 168 et seq.
- particles of fluoropolymers are applied to metal surfaces, whereby a markedly reduced wettability of the surfaces thus produced to water has been determined with a considerably reduced tendency to freeze.
- WO 00/58410 describes the structures and claims the formation thereof by spraying hydrophobic alcohols such as nonakosan-10-ol or alkanediols such as nonakosan-5,10-diol.
- hydrophobic alcohols such as nonakosan-10-ol or alkanediols such as nonakosan-5,10-diol.
- the disadvantage here is the lack of stability of the self-cleaning surfaces, since detergents lead to the replacement of the structure.
- EP 1 040 874 A2 describes the imprinting of microstructures and claims the use of such structures in analytics (microfluidics). A disadvantage of these structures is the insufficient mechanical stability.
- EP 0 934 865 A2 describes a water repellant product and its preparation wherein the debris repellent surface is prepared by applying a film to the surface to be treated comprising fine particles of metal oxide and the hydrolyzate of a metal alkoxide or chelate. To solidify this film, the substrate to which the film has been applied must be sintered at temperatures above 400 ° C. The method can therefore only be used for substrates which are stable even at temperatures above 400 ° C.
- the object of the present invention was to provide particularly well self-cleaning surfaces with structures in the nanometer range, as well as a simple method for producing such self-cleaning surfaces.
- an object of the present invention to provide a method for producing self-cleaning surfaces, in which the coated material must be exposed to only low chemical or physical loads.
- the subject matter of the present invention is therefore a self-cleaning surface according to at least one of claims 1 to 7, which has an artificial, at least partially hydrophobic surface structure of elevations and depressions, which is characterized in that the elevations and depressions are defined by structure-forming particles fixed on the surface, which have a fissured structure with elevations and / or depressions in the nanometer range and hydrophobic properties, and the Fixierstoffpumble used for fixing are formed, which thus also contribute to the formation of the elevations and depressions, wherein the surfaces of the Fixierstoffpizate with adjacent surfaces of Fixierstoffpumblen and / or structure-forming particles at least partially adhere to each other, so that the structure is maintained in the nanometer range of the structure-forming particles.
- self-cleaning surfaces are accessible which have structure-forming particles and fixing agent particles which together form the desired surface structure.
- particles which have a fissured structure surfaces are accessible in a simple manner, which are structured down to the nanometer range. In order to obtain this structure in the nanometer range, it is necessary that the particles are not significantly wetted by the fixer particles with which they are fixed to the surface, otherwise the structure would be lost in the nano range.
- the self-cleaning surface of the invention which has an artificial, at least partially hydrophobic surface structure of elevations and depressions, is characterized in that the elevations and depressions by structure-forming particles fixed on the surface, which have a fissured structure with elevations and / or depressions in the nanometer range and have hydrophobic properties, and the Fixierstoffpumble used for fixing are formed, which thus also contribute to the formation of the elevations and depressions, wherein the surfaces of the Fixierstoffp maybe adhere to adjacent surfaces of Fixierstoffp personalityn and / or structure-forming particles at least partially together, so that the structure in the nanometer range the structure-forming particles is retained.
- the structure-forming particles preferably have elevations with a height of on average 20 to 500 nm, more preferably of 50 to 200 nm.
- the spacing of these elevations or depressions on the particles is preferably less than 500 nm, very particularly preferably less than 200 nm.
- the self-cleaning surfaces have the structure-forming particles on the surface preferably at intervals of 0-10 particle diameter, in particular at intervals of 0. 3 and most preferably from 1 - 2 particle diameter, on.
- the rugged structures with elevations and / or depressions in the nanometer range can be formed, for example, via cavities, pores, grooves, points and / or points.
- the particles themselves have an average size of less than 50 .mu.m, preferably of less than 30 .mu.m and most preferably of less than 20 .mu.m.
- the dibutyl phthalate adsorption based on DIN 53 601, provides values between 100 and 350 ml / 100 g, preferably values between 250 and 350 ml / 100 g.
- the structure-forming particles preferably have a BET surface area of from 50 to 600 square meters per gram. Most preferably, the particles have a BET surface area of 50 to 200 m 2 / g.
- the particles comprise at least one material selected from silicates, doped silicates, minerals, metal oxides, silicas, polymers, coated metal powders.
- the particles very particularly preferably have pyrogenic silicic acids or precipitated silicas, in particular aerosils, Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , zinc powder encased with Aerosil R 974 or pulverulent polymers, for example cryogenically ground or spray-dried polytetrafluoroethylene (PTFE).
- PTFE polytetrafluoroethylene
- the fixed particles of the self-cleaning surfaces have not only the fissured structures but also hydrophobic properties.
- the particles may themselves be hydrophobic, e.g. PTFE-containing particles.
- the hydrophobing of the fixed particles can also be carried out subsequently in a manner known to the person skilled in the art.
- Fixierstoffp include compounds selected from the group of hot melt adhesives and / or powder coatings. These hot melt adhesives and / or powder coatings are particularly preferably selected from the ethylene / ethyl acrylate copolymers, ethylene / vinyl acetate copolymers, polyamides, epoxy resins, polyethersulfones, polyisobutenes or polyvinyl butyrals. More particularly, the hot melt adhesive used as a fixing agent is a copolymer of thermoplastic polyamide with caprolactone.
- the fixer particles preferably have an average size of less than 50 microns.
- the fixer particles preferably have an average size which corresponds to the size of the structure-forming particles. But it can also be advantageous if the Fixing agent particles have a from 10 to 70%, preferably 25 to 50% smaller average size than that of the structure-forming particles.
- the self-cleaning surfaces according to the invention have an unrolling angle of less than 20 °, particularly preferably less than 10 °, the unrolling angle being defined such that a drop of water applied from a 1 cm height rolls onto a plane surface resting on an inclined plane.
- the advance angle and the retraction angle are preferably above 140 °, more preferably above 150 ° and have a hysteresis of less than 10 °.
- the self-cleaning surfaces are semitransparent.
- the surfaces according to the invention can be contact-transparent, that is to say that after the creation of a surface according to the invention on a labeled object, this inscription, depending on the size of the writing, can still be read.
- the self-cleaning surfaces according to the invention are produced by the process according to the invention for producing these surfaces.
- such structure-forming particles which comprise at least one material selected from silicates, doped silicates, minerals, metal oxides, silicic acids or polymers are used.
- the particles have fumed silicates or silicas, especially aerosils, Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 coated with Aerosil R 974 Zn powder or powdery polymers, such as cryogenically ground or spray-dried polytetrafluoroethylene (PTFE), on.
- PTFE polytetrafluoroethylene
- Particles that have fissured structures with elevations and / or pits in the nanometer range are used. In this way, self-cleaning surfaces are accessible, which have a particularly good self-cleaning behavior.
- the particles for generating the self-cleaning surfaces have, in addition to the fissured structures, also hydrophobic properties.
- the particles themselves may be hydrophobic, e.g. PTFE-containing particles, or the particles used may have been rendered hydrophobic.
- the hydrophobing of the particles can be carried out in a manner known to those skilled in the art.
- Typical hydrophobized particles are e.g. Fine powders such as Aerosil-VPR 411, Aerosil R 974 or Aerosil-R 8200 (Degussa AG), which are available for purchase.
- the fixing agents used as fixing agent are preferably compounds selected from the group of hot melt adhesives and / or powder coatings. These hot melt adhesives and / or powder coatings preferably comprise at least one compound selected from the ethylene / ethyl acrylate copolymers, ethylene / vinyl acetate copolymers, polyamides, polyethersulfones, polyisobutenes, epoxy resins or polyvinyl butyrals.
- melting or else sintering is to be understood as meaning the sticking together of fixing agent particles at their points of contact.
- the particles may be applied to the surface in a manner known to those skilled in the art, for example by spraying or powdering.
- the surface may already have anticorrosive, color or warning coatings.
- melt melting or else sintering being understood to mean softening of the fixing agent particles such that the surface of the fixing agent particles has adjacent surfaces of fixing agent particles and / or structure-forming particles and of the surface of the object, which is self-cleaning Surface is provided, after cooling at least partially adhere to each other.
- the adhesion may have been produced by chemical bonding but also by physical forces.
- the temperature at which the melting is carried out, as well as the duration of the melting are to be chosen so that the fixer particles only partially melt and the structure, in particular the structure in the nanometer range, of the structure-forming particles is maintained.
- the heating may be carried out in a manner known to those skilled in the art, e.g. by means of a furnace or other heat source. Preferably, the heating takes place by means of infrared radiation.
- the structure-forming particles can at least partially be firmly bound to the fixing agent particles without the remelting of the structure-forming particles by the fixing agent taking place, as a result of which the structure of the structure-forming particles in the nanometer range would be lost.
- the fixing agent particles used according to the invention preferably have an average size of less than 50 ⁇ m.
- the fixer particles preferably have an average size which corresponds to the size of the structure-forming particles.
- the fixing agent particles can also be advantageous if the fixing agent particles have a size which is smaller by 10 to 70%, preferably 25 to 50%, than that of the structure-forming particles.
- hydrophilic structure-forming particles with hydrophilic fixing agent particles are used to produce the self-cleaning surface structure, it is treated with at least one compound from the group of the alkylsilanes, alkyldisilazanes, waxes, paraffins, fatty acid esters, fluorinated and / or functionalized alkanes or perfluoroalkylsilanes, around the self-cleaning surface with hydrophobic Equip features.
- the treatment is carried out by subjecting the particle-bearing surface to be hydrophobicized to a solution containing a hydrophobing reagent, such as e.g.
- Alkylsilane has, is dipped, excess hydrophobing reagent is drained and the surface is annealed at the highest possible temperature.
- the treatment can also be done by spraying the surface with a medium having a hydrophobizing reagent and subsequent heat treatment.
- Such a treatment is e.g. for the treatment of steel beams or other heavy or bulky objects.
- the limitation of the temperature is limited by the softening temperatures of the fixing agents, the structure-forming particles and the substrate to which the self-cleaning surface has been applied.
- the process according to at least one of claims 8 to 15 can be used excellently for producing self-cleaning surfaces on planar or non-planar objects, in particular on non-planar objects. This is only possible to a limited extent with the conventional methods. In particular, by methods in which prefabricated films are applied to a surface or in processes in which a structure is to be created by embossing, non-planar objects, such as sculptures, are not or only partially accessible. Naturally, the inventive method but also for the production of self-cleaning surfaces can be used on objects with planar surfaces, such as greenhouses or public transport.
- the application of the method according to the invention for the production of self-cleaning surfaces on greenhouses has advantages, since with the method self-cleaning surfaces can be made, for example, on transparent materials such as glass or Plexiglas ® and the self-cleaning surface can be formed at least as far transparent that for the Growth of the plants in the greenhouse can penetrate enough sunlight through the provided with a self-cleaning surface transparent surface.
- greenhouses which regularly have to be cleaned of deciduous, dust, lime and biological material, such as algae
- greenhouses having a surface according to the invention according to one of claims 1 to 7, operated with longer cleaning intervals become.
- the inventive method for finishing load-bearing or non-structural elements of building construction with self-cleaning surfaces especially if a corrosion protection, a signal marking, such as yellow-black striped warning signs or a color coating having used.
- a corrosion protection such as yellow-black striped warning signs or a color coating having used.
- the method of the invention may also be used to make self-cleaning surfaces on non-rigid surfaces of articles, such as e.g. Umbrellas or other surfaces that are kept flexible.
- the process according to the invention according to at least one of claims 8 to 15 can be used for producing self-cleaning surfaces on flexible or inflexible walls in the sanitary sector.
- Such walls can e.g. Partitions in public toilets, walls of shower cubicles, swimming pools or saunas, but also shower curtains (flexible wall) be.
- PMMA polymethyl methacrylate
- PMMA polymethyl methacrylate
- a spray-dried fumed silica having a BET surface area of 90 m 2 / g a spray-dried fumed silica having a BET surface area of 90 m 2 / g
- 50 wt. % Polyamide hot-melt adhesive powder Vestamelt P06, Degussa AG
- the plate is annealed at 108 ° C for 5 min. Subsequently, the plate with Antispread ® (Dr.
- a surface hydrophobizing agent is treated so that the hydrophobicity of the particles, or the surface is adjusted.
- the characterization of the surface was initially visual and is logged with +++. +++ means, water droplets are almost completely formed. Progressive and retreatment angles greater than 150 ° each were measured. The associated hysteresis is below 10 °.
- a powder coating (FREOPOX EKP-7, Emil Frei GmbH & Co.) was cold-doctored to a 200 ⁇ m thick layer on a nickel sheet and sprinkled with a hydrophobic Aerosil (R 8200, Degussa AG). This mixture and the nickel sheet were exposed to a temperature of 180 ° C for 3 minutes. After cooling, only a slight improvement in the bead behavior of water was observed.
- Example 1 The experiment of Example 1 was repeated, but the Aerosil R 8200 was pressed by means of a metal roller into the molten paint. It was re-tempered for another 3 minutes. The cooled plate shows only a slightly improved Abperl compared to the pure powder coating.
- Example 1 The experiment of Example 1 was repeated, but instead of the powder coating a hot melt adhesive (Vestamelt P 06, Degussa AG) was used. After cooling, only a slight improvement in the bead behavior of water was observed.
- a hot melt adhesive Vestamelt P 06, Degussa AG
- Example 1 The experiment of Example 1 was repeated. However, instead of the hydrophobic Aerosils R 8200, a hydrophilic silica (Sipernat 350, Degussa AG) was used. After cooling, the plate by means of a hydrophobicizing reagent (Antispread ®, Dr. Tillwich GmbH) was rendered hydrophobic subsequently. The lotus effect was fully developed in this example.
- the surface is evaluated only with +, ie, the droplet forms poorly and sticks to high angles of inclination at the surface.
- the bad lotus effect in the comparative example is due to smearing of the fissured structure. This is done by dissolving monomers in ethanol. Before curing, the ethanol evaporates and the hardener preferably remains in the fissured structures.
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Abstract
Description
Die vorliegende Erfindung betrifft selbstreinigende Oberflächen und Verfahren zu deren Herstellung.The present invention relates to self-cleaning surfaces and methods for their production.
Gegenstände mit extrem schwer benetzbaren Oberflächen weisen eine Reihe von wirtschaftlich bedeutsamen Merkmalen auf. Das wirtschaftlich bedeutendste Merkmal ist dabei die selbstreinigende Wirkung von schwerbenetzbaren Oberflächen, da die Reinigung von Oberflächen zeit- und kostenintensiv ist. Selbstreinigende Oberflächen sind somit von höchstem wirtschaftlichen Interesse. Haftmechanismen werden in der Regel durch grenzflächenenergetische Parameter zwischen den beiden sich berührenden Oberflächen bedingt. In der Regel versuchen dabei die Systeme ihre freie Grenzflächenenergie zu erniedrigen. Liegen die freien Grenzflächenenergien zwischen zwei Komponenten von sich aus schon sehr niedrig, so kann allgemein davon ausgegangen werden, dass die Haftung zwischen diesen beiden Komponenten schwach ausgeprägt ist. Wichtig ist dabei die relative Erniedrigung der freien Grenzflächenenergie. Bei Paarungen mit einer hohen und einer niedrigen Grenzflächenenergie kommt es sehr oft auf die Möglichkeiten der Wechselwirkungen an. So ist beispielsweise beim Aufbringen von Wasser auf eine hydrophobe Oberfläche nicht möglich, eine merkliche Erniedrigung der Grenzflächenenergie herbeizuführen. Dies ist daran erkennbar, dass die Benetzung schlecht ist. Aufgebrachtes Wasser bildet Tropfen mit sehr hohem Kontaktwinkel. Perfluorierte Kohlenwasserstoffe, z.B. Polytetrafluorethylen, haben sehr niedrige Grenzflächenenergie. Auf solchen Oberflächen haften kaum irgendwelche Komponenten bzw. auf solchen Oberflächen abgelagerte Komponenten können sehr leicht wieder entfernt werden.Articles having extremely difficult to wet surfaces have a number of economically important features. The economically most important feature is the self-cleaning effect of difficult-to-wet surfaces, since the cleaning of surfaces is time consuming and costly. Self-cleaning surfaces are therefore of the highest economic interest. Adhesive mechanisms are usually conditioned by interfacial energy parameters between the two contacting surfaces. As a rule, the systems try to lower their free surface energy. If the free interfacial energies between two components are inherently very low, it can generally be assumed that the adhesion between these two components is weak. Important here is the relative lowering of the free surface energy. For pairings with high and low interfacial energy, the possibilities of interactions are very often important. For example, when water is applied to a hydrophobic surface, it is not possible to bring about a marked lowering of the interfacial energy. This is evident from the fact that the wetting is bad. Applied water forms drops with a very high contact angle. Perfluorinated hydrocarbons, e.g. Polytetrafluoroethylene, have very low interfacial energy. Hardly any components adhere to such surfaces or components deposited on such surfaces can be removed very easily.
Der Einsatz von hydrophoben Materialien, wie perfluorierten Polymeren, zur Herstellung von hydrophoben Oberflächen ist bekannt. Eine Weiterentwicklung dieser Oberflächen besteht darin, die Oberflächen im µm-Bereich bis nm-Bereich zu strukturieren.
In
Dieses Prinzip ist der Natur entlehnt. Kleine Kontaktflächen erniedrigen die Van-der-Waal's-Wechselwirkung, die für die Haftung an ebenen Oberflächen mit niedriger Oberflächenenergie verantwortlich ist. Beispielsweise sind die Blätter der Lotus-Pflanze mit Erhebungen aus einem Wachs versehen, die die Kontaktfläche zu Wasser herabsetzen.
Eine weitere Methode, leicht reinigbare Oberflächen zu erzeugen, ist in
In
Aufgabe der vorliegenden Erfindung war die Bereitstellung von besonders gut selbstreinigenden Oberflächen mit Strukturen im Nanometerbereich, sowie ein einfaches Verfahren zur Herstellung solcher selbstreinigenden Oberflächen.The object of the present invention was to provide particularly well self-cleaning surfaces with structures in the nanometer range, as well as a simple method for producing such self-cleaning surfaces.
Außerdem war Aufgabe der vorliegenden Erfindung ein Verfahren zur Herstellung von selbstreinigenden Oberflächen bereitzustellen, bei denen das beschichtete Material nur geringen chemischen oder physikalischen Belastungen ausgesetzt werden muss.In addition, an object of the present invention to provide a method for producing self-cleaning surfaces, in which the coated material must be exposed to only low chemical or physical loads.
Gegenstand der vorliegenden Erfindung ist deshalb eine selbstreinigende Oberfläche gemäß zumindest einem der Ansprüche 1 bis 7, die eine künstliche, zumindest teilweise hydrophobe Oberflächenstruktur aus Erhebungen und Vertiefungen aufweist, welche dadurch gekennzeichnet ist, dass die Erhebungen und Vertiefungen durch auf der Oberfläche fixierte strukturbildende Partikel, die eine zerklüftete Struktur mit Erhebungen und/oder Vertiefungen im Nanometerbereich und hydrophobe Eigenschaften aufweisen, sowie die zur Fixierung eingesetzten Fixiermittelpartikel gebildet werden, die somit ebenfalls zur Bildung der Erhebungen und Vertiefungen beitragen, wobei die Oberflächen der Fixiermittelpartikel mit benachbarten Oberflächen von Fixiermittelpartikeln und/oder strukturbildenden Partikeln zumindest teilweise aneinander haften, so dass die Struktur im Nanometerbereich der strukturbildenden Partikeln erhalten bleibt.The subject matter of the present invention is therefore a self-cleaning surface according to at least one of claims 1 to 7, which has an artificial, at least partially hydrophobic surface structure of elevations and depressions, which is characterized in that the elevations and depressions are defined by structure-forming particles fixed on the surface, which have a fissured structure with elevations and / or depressions in the nanometer range and hydrophobic properties, and the Fixiermittelpartikel used for fixing are formed, which thus also contribute to the formation of the elevations and depressions, wherein the surfaces of the Fixiermittelpartikel with adjacent surfaces of Fixiermittelpartikeln and / or structure-forming particles at least partially adhere to each other, so that the structure is maintained in the nanometer range of the structure-forming particles.
Ebenfalls ist Gegenstand der vorliegenden Erfindung ein Verfahren gemäß zumindest einem der Ansprüche 8 bis 15 zur Herstellung von selbstreinigenden Oberflächen gemäß zumindest einem der Ansprüche 1 bis 7, die eine künstliche, zumindest teilweise hydrophobe Oberflächenstruktur aus Erhebungen und Vertiefungen aufweisen, wobei die Erhebungen und Vertiefungen durch an der Oberfläche fixierte strukturbildende Partikel gebildet werden, dadurch gekennzeichnet, dass die strukturbildenden Partikel, die eine zerklüftete Struktur mit Erhebungen und/oder Vertiefungen im Nanometerbereich und hydrophobe Eigenschaften aufweisen, an der Oberfläche durch Fixiermittelpartikel fixiert werden, die ebenfalls zur Bildung der Erhebungen und Vertiefungen beitragen, und dass das Verfahren die folgenden Schritte umfasst:
- a) Aufbringen von Fixiermittelpartikeln und strukturbildenden Partikeln, auf eine Oberfläche, wobei zuerst die Fixiermittelpartikel und anschließend die strukturbildenden Partikel auf die Oberfläche aufgebracht werden und
- b) Anschmelzen der Fixiermittelpartikel zur Fixierung der strukturbildenden Partikel und der Fixiermittelpartikel auf der Oberfläche durch kurzzeitiges Erwärmen, wobei die Temperatur, bei der das Anschmelzen durchgeführt wird, und die Dauer des Anschmelzens so zu wählen sind, dass die Fixiermittelpartikel nur teilweise verschmelzen, wobei die Fixiermittelpartikel an ihren Berührungspunkten zusammenkleben und die Struktur, insbesondere die Struktur im Nanometerbereich, der strukturbildenden Partikel erhalten bleibt
- a) applying Fixiermittelpartikeln and structure-forming particles, on a surface, wherein first the Fixiermittelpartikel and then the structure-forming particles are applied to the surface and
- b) melting the fixing agent particles for fixing the structure-forming particles and the fixing agent particles on the surface by brief heating, wherein the temperature at which the melting is carried out, and the duration of the melting are to be selected so that the fixing agent particles only partially fuse, wherein the Stick together Fixiermittelpartikel at their points of contact and the structure, in particular the structure in the nanometer range, the structure-forming particles is maintained
Durch das erfindungsgemäße Verfahren sind selbstreinigende Oberflächen zugänglich, die strukturbildende Partikel und Fixiermittelpartikel aufweisen, die gemeinsam die gewünschte Oberflächenstruktur bilden. Durch die Verwendung von Partikeln, welche eine zerklüftete Struktur aufweisen, werden auf einfache Weise Oberflächen zugänglich, die bis in den Nanometerbereich strukturiert sind. Um diese Struktur im Nanometerbereich zu erhalten ist es notwendig, dass die Partikel nicht wesentlich durch die Fixiermittelpartikel, mit welchen sie an der Oberfläche fixiert sind, benetzt sind, da sonst die Struktur im Nanobereich verloren gehen würde.By means of the method according to the invention, self-cleaning surfaces are accessible which have structure-forming particles and fixing agent particles which together form the desired surface structure. By using particles which have a fissured structure, surfaces are accessible in a simple manner, which are structured down to the nanometer range. In order to obtain this structure in the nanometer range, it is necessary that the particles are not significantly wetted by the fixer particles with which they are fixed to the surface, otherwise the structure would be lost in the nano range.
Die erfindungsgemäßen selbstreinigenden Oberflächen sowie ein Verfahren zu deren Herstellung werden im folgenden beispielhaft beschrieben, wobei die erfindungsgemäßen Oberflächen und das erfindungsgemäße Verfahren nicht auf die beispielhaften Ausführungsformen beschränkt sein sollenThe self-cleaning surfaces of the invention and a process for their preparation are described below by way of example, wherein the surfaces according to the invention and the inventive method should not be limited to the exemplary embodiments
Die erfindungsgemäße selbstreinigende Oberfläche, die eine künstliche, zumindest teilweise hydrophobe Oberflächenstruktur aus Erhebungen und Vertiefungen aufweist, zeichnet sich dadurch aus, dass die Erhebungen und Vertiefungen durch auf der Oberfläche fixierte strukturbildende Partikel, die eine zerklüftete Struktur mit Erhebungen und/oder Vertiefungen im Nanometerbereich und hydrophobe Eigenschaften aufweisen, sowie die zur Fixierung eingesetzten Fixiermittelpartikel gebildet werden, die somit ebenfalls zur Bildung der Erhebungen und Vertiefungen beitragen, wobei die Oberflächen der Fixiermittelpartikel mit benachbarten Oberflächen von Fixiermittelpartikeln und/oder strukturbildenden Partikeln zumindest teilweise aneinander haften, so dass die Struktur im Nanometerbereich der strukturbildenden Partikeln erhalten bleibt.The self-cleaning surface of the invention, which has an artificial, at least partially hydrophobic surface structure of elevations and depressions, is characterized in that the elevations and depressions by structure-forming particles fixed on the surface, which have a fissured structure with elevations and / or depressions in the nanometer range and have hydrophobic properties, and the Fixiermittelpartikel used for fixing are formed, which thus also contribute to the formation of the elevations and depressions, wherein the surfaces of the Fixiermittelpartikel adhere to adjacent surfaces of Fixiermittelpartikeln and / or structure-forming particles at least partially together, so that the structure in the nanometer range the structure-forming particles is retained.
Vorzugsweise weisen die strukturbildenden Partikel Erhöhungen mit einer Höhe von im Mittel 20 bis 500 nm, besonders bevorzugt von 50 bis 200 nm auf. Der Abstand dieser Erhöhungen bzw. Vertiefungen auf den Partikeln beträgt vorzugsweise weniger als 500 nm, ganz besonders bevorzugt weniger als 200 nm. Die selbstreinigenden Oberflächen weisen die strukturbildenden Partikel auf der Oberfläche vorzugsweise in Abständen von 0 - 10 Partikeldurchmesser, insbesondere in Abständen von 0 - 3 und ganz besonders bevorzugt von 1 - 2 Partikeldurchmesser, auf.The structure-forming particles preferably have elevations with a height of on average 20 to 500 nm, more preferably of 50 to 200 nm. The spacing of these elevations or depressions on the particles is preferably less than 500 nm, very particularly preferably less than 200 nm. The self-cleaning surfaces have the structure-forming particles on the surface preferably at intervals of 0-10 particle diameter, in particular at intervals of 0. 3 and most preferably from 1 - 2 particle diameter, on.
Die zerklüfteten Strukturen mit Erhebungen und/oder Vertiefungen im Nanometerbereich können z.B. über Hohlräume, Poren, Riefen, Spitzen und/oder Zacken gebildet werden. Die Partikel selbst weisen eine durchschnittliche Größe von kleiner 50 µm, vorzugsweise von kleiner 30 µm und ganz besonders bevorzugt von kleiner 20 µm auf. Die Dibutylphthalat-Adsorbption, angelehnt an DIN 53 601, liefert Werte zwischen 100 und 350 ml/100 g, bevorzugt Werte zwischen 250 und 350 ml/100 g.The rugged structures with elevations and / or depressions in the nanometer range can be formed, for example, via cavities, pores, grooves, points and / or points. The particles themselves have an average size of less than 50 .mu.m, preferably of less than 30 .mu.m and most preferably of less than 20 .mu.m. The dibutyl phthalate adsorption, based on DIN 53 601, provides values between 100 and 350 ml / 100 g, preferably values between 250 and 350 ml / 100 g.
Bevorzugt weisen die strukturbildenden Partikel eine BET-Oberfläche von 50 bis 600 Quadratmeter pro Gramm auf. Ganz besonders bevorzugt weisen die Partikel eine BET-Oberfläche von 50 bis 200 m2/g auf.The structure-forming particles preferably have a BET surface area of from 50 to 600 square meters per gram. Most preferably, the particles have a BET surface area of 50 to 200 m 2 / g.
Als strukturbildende Partikel können verschiedenste Verbindungen aus vielen Bereichen der Chemie und/oder der Natur eingesetzt werden. Vorzugsweise weisen die Partikel zumindest ein Material, ausgewählt aus Silikaten, dotierten Silikaten, Mineralien, Metalloxiden, Kieselsäuren, Polymeren, beschichteten Metallpulvern auf. Ganz besonders bevorzugt weisen die Partikel pyrogene Kieselsäuren oder Fällungskieselsäuren, insbesondere Aerosile, Al2O3, SiO2, TiO2, ZrO2, mit Aerosil R974 ummanteltes Zinkpulver oder pulverförmige Polymere, wie z.B. kryogen gemahlenes oder sprühgetrocknetes Polytetrafluorethylen (PTFE), auf.As structure-forming particles, a wide variety of compounds from many fields of chemistry and / or nature can be used. Preferably, the particles comprise at least one material selected from silicates, doped silicates, minerals, metal oxides, silicas, polymers, coated metal powders. The particles very particularly preferably have pyrogenic silicic acids or precipitated silicas, in particular aerosils, Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , zinc powder encased with Aerosil R 974 or pulverulent polymers, for example cryogenically ground or spray-dried polytetrafluoroethylene (PTFE).
Die fixierten Partikel der selbstreinigenden Oberflächen weisen neben den zerklüfteten Strukturen auch hydrophobe Eigenschaften auf. Die Partikel können dabei aber selbst hydrophob sein, wie z.B. PTFE aufweisende Partikel. Das Hydrophobieren der fixierten Partikel kann aber auch nachträglich auf eine dem Fachmann bekannte Weise erfolgt sein.The fixed particles of the self-cleaning surfaces have not only the fissured structures but also hydrophobic properties. The particles may themselves be hydrophobic, e.g. PTFE-containing particles. However, the hydrophobing of the fixed particles can also be carried out subsequently in a manner known to the person skilled in the art.
Die erfindungsgemäß vorhandenen Fixiermittelpartikel umfassen Verbindungen ausgewählt aus der Gruppe der Schmelzkleber und/oder Pulverlacke. Besonders bevorzugt werden diese Schmelzkleber und/oder Pulverlacke ausgewählt aus den Ethylen/Ethylacrylat-Copolymeren, Ethylen/Vinylacetat-Copolymeren, Polyamiden, Epoxydharze, Polyethersulfonen, Polyisobutenen oder Polyvinylbutyralen. Ganz besonders ist der als Fixiermittel verwendete Schmelzkleber ein Copolymer aus thermoplastischem Polyamid mit Caprolacton.The present invention Fixiermittelpartikel include compounds selected from the group of hot melt adhesives and / or powder coatings. These hot melt adhesives and / or powder coatings are particularly preferably selected from the ethylene / ethyl acrylate copolymers, ethylene / vinyl acetate copolymers, polyamides, epoxy resins, polyethersulfones, polyisobutenes or polyvinyl butyrals. More particularly, the hot melt adhesive used as a fixing agent is a copolymer of thermoplastic polyamide with caprolactone.
Die Fixiermittelpartikel weisen vorzugsweise eine durchschnittliche Größe von kleiner 50 µm auf. Bevorzugt weisen die Fixiermittelpartikel eine durchschnittliche Größe die der Größe der strukturbildenden Partikel entspricht auf. Es kann aber auch vorteilhaft sein, wenn die Fixiermittelpartikel eine von 10 bis 70 %, vorzugsweise 25 bis 50 % kleinere durchschnittliche Größe als die der strukturbildenden Partikel aufweisen.The fixer particles preferably have an average size of less than 50 microns. The fixer particles preferably have an average size which corresponds to the size of the structure-forming particles. But it can also be advantageous if the Fixing agent particles have a from 10 to 70%, preferably 25 to 50% smaller average size than that of the structure-forming particles.
Die erfindungsgemäßen selbstreinigenden Oberflächen weisen eine Abrollwinkel von kleiner 20 °, besonders bevorzugt kleiner 10° auf, wobei der Abrollwinkel so definiert ist, dass ein aus 1 cm Höhe auf eine auf einer schiefen Ebene ruhenden planen Oberfläche aufgebrachter Wassertropfen abrollt. Die Fortschreitwinkel und die Rückzugswinkel liegen bevorzugt oberhalb von 140°, besonders bevorzugt oberhalb von 150° und weisen eine Hysterese von kleiner 10° auf.The self-cleaning surfaces according to the invention have an unrolling angle of less than 20 °, particularly preferably less than 10 °, the unrolling angle being defined such that a drop of water applied from a 1 cm height rolls onto a plane surface resting on an inclined plane. The advance angle and the retraction angle are preferably above 140 °, more preferably above 150 ° and have a hysteresis of less than 10 °.
Je nach verwendeten Fixiermittelpartikeln und je nach Größe und Material der eingesetzten strukturbildenden Partikel kann erreicht werden, dass die selbstreinigenden Oberflächen semitransparent sind. Insbesondere können die erfindungsgemäßen Oberflächen kontakttransparent sein, dass heißt das nach Erstellen einer erfindungsgemäßen Oberfläche auf einem beschrifteten Gegenstand diese Beschriftung, in Abhängigkeit von der Größe der Schrift, weiterhin lesbar ist. Je feiner die verwendeten Partikel sind, desto besser sind die transparenten Eigenschaften der selbstreinigenden Oberflächen.Depending on the used Fixiermittelpartikeln and depending on the size and material of the structure-forming particles used can be achieved that the self-cleaning surfaces are semitransparent. In particular, the surfaces according to the invention can be contact-transparent, that is to say that after the creation of a surface according to the invention on a labeled object, this inscription, depending on the size of the writing, can still be read. The finer the particles used, the better the transparent properties of the self-cleaning surfaces.
Die erfindungsgemäßen selbstreinigenden Oberflächen werden durch das erfindungsgemäße Verfahren zur Herstellung dieser Oberflächen hergestellt. Dieses erfindungsgemäße Verfahren zur Herstellung von selbstreinigenden Oberflächen gemäß zumindest einem der Ansprüche 1 bis 7, die eine künstliche, zumindest teilweise hydrophobe Oberflächenstruktur aus Erhebungen und Vertiefungen aufweisen, wobei die Erhebungen und Vertiefungen durch an der Oberfläche fixierte strukturbildende Partikel gebildet werden, zeichnet sich dadurch aus, dass die strukturbildenden Partikel, die eine zerklüftete Struktur mit Erhebungen und/oder Vertiefungen im Nanometerbereich und hydrophobe Eigenschaften aufweisen, an der Oberfläche durch Fixiermittelpartikel fixiert werden, die ebenfalls zur Bildung der Erhebungen und Vertiefungen beitragen.
Vorzugsweise werden solche strukturbildenden Partikel, die zumindest ein Material, ausgewählt aus Silikaten, dotierten Silikaten, Mineralien, Metalloxiden, Kieselsäuren oder Polymeren aufweisen, eingesetzt. Ganz besonders bevorzugt weisen die Partikel pyrogene Silikate oder Kieselsäuren, insbesondere Aerosile, Al2O3, SiO2, TiO2, ZrO2 mit Aerosil R 974 ummanteltes
Zn-Pulver oder pulverförmige Polymere, wie z.B. kryogen gemahlenes oder sprühgetrocknet Polytetrafluorethylen (PTFE), auf.The self-cleaning surfaces according to the invention are produced by the process according to the invention for producing these surfaces. This inventive method for producing self-cleaning surfaces according to at least one of claims 1 to 7, which have an artificial, at least partially hydrophobic surface structure of elevations and depressions, wherein the elevations and depressions are formed by fixed to the surface structure-forming particles, characterized by characterized in that the structure-forming particles, which have a fissured structure with elevations and / or depressions in the nanometer range and hydrophobic properties, are fixed to the surface by fixing agent particles, which also contribute to the formation of the elevations and depressions.
Preferably, such structure-forming particles which comprise at least one material selected from silicates, doped silicates, minerals, metal oxides, silicic acids or polymers are used. Most preferably, the particles have fumed silicates or silicas, especially aerosils, Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 coated with Aerosil R 974
Zn powder or powdery polymers, such as cryogenically ground or spray-dried polytetrafluoroethylene (PTFE), on.
Es werden Partikel, die zerklüftete Strukturen mit Erhebungen und/oder Vertiefungen im Nanometerbereich aurweisen, eingesetzt. Auf diese Weise sind selbstreinigende Oberflächen zugänglich, die ein besonders gutes Selbstreinigungsverhalten aufweisen. Bevorzugt werden Partikel mit einer BET-Oberfläche von 50 bis 600 m2/g eingesetzt. Besonders bevorzugt werden Partikel eingesetzt, die eine BET-Oberfläche von 50 bis 200 m2/g aufweisen.Particles that have fissured structures with elevations and / or pits in the nanometer range are used. In this way, self-cleaning surfaces are accessible, which have a particularly good self-cleaning behavior. Preference is given to using particles having a BET surface area of from 50 to 600 m 2 / g. Particular preference is given to using particles which have a BET surface area of 50 to 200 m 2 / g.
Die Partikel zur Generierung der selbstreinigenden Oberflächen weisen neben den zerklüfteten Strukturen auch hydrophobe Eigenschaften auf. Die Partikel können selbst hydrophob sein, wie z.B. PTFE aufweisende Partikel, oder die eingesetzten Partikel können hydrophobiert worden sein. Das Hydrophobieren der Partikel kann auf eine dem Fachmann bekannte Weise erfolgen. Typische hydrophobierte Partikel sind z.B. Feinstpulver wie Aerosil-VPR 411, Aerosil R 974 oder Aerosil-R 8200 (Degussa AG), die käuflich zu erwerben sind.The particles for generating the self-cleaning surfaces have, in addition to the fissured structures, also hydrophobic properties. The particles themselves may be hydrophobic, e.g. PTFE-containing particles, or the particles used may have been rendered hydrophobic. The hydrophobing of the particles can be carried out in a manner known to those skilled in the art. Typical hydrophobized particles are e.g. Fine powders such as Aerosil-VPR 411, Aerosil R 974 or Aerosil-R 8200 (Degussa AG), which are available for purchase.
Die als Fixiermittelpartikel eingesetzten Fixiermittel sind vorzugsweise Verbindungen, ausgewählt aus der Gruppe der Schmelzkleber und/oder Pulverlacke. Diese Schmelzkleber und/oder Pulverlacke weisen vorzugsweise zumindest eine Verbindung, ausgewählt aus den Ethylen/Ethylacrylat-Copolymeren, Ethylen/Vinylacetat-Copolymeren, Polyamiden, Polyethersulfonen, Polyisobutenen, Epoxydharze oder Polyvinylbutyralen auf.The fixing agents used as fixing agent are preferably compounds selected from the group of hot melt adhesives and / or powder coatings. These hot melt adhesives and / or powder coatings preferably comprise at least one compound selected from the ethylene / ethyl acrylate copolymers, ethylene / vinyl acetate copolymers, polyamides, polyethersulfones, polyisobutenes, epoxy resins or polyvinyl butyrals.
Das erfindungsgemäße Verfahren umfasst die Schritte
- a) Aufbringen von Fixiermittelpartikeln und strukturbildenden Partikeln, auf eine Oberfläche, wobei zuerst die Fixiermittelpartikel und anschließend die strukturbildenden Partikel auf die Oberfläche aufgebracht werden, und
- b) Anschmelzen der Fixiermittelpartikel zur Fixierung der strukturbildenden Partikel und der Fixiermittelpartikel auf der Oberfläche durch kurzzeitiges Erwärmen, wobei die Temperatur, bei der das Anschmelzen durchgeführt wird, und die Dauer des Anschmelzens so zu wählen sind, dass die Fixiermittelpartikel nur teilweise verschmelzen, wobei die Fixiermittelpartikel an ihren Berührungspunkten zusammenkleben und die Struktur, insbesondere die Struktur im Nanometerbereich, der strukturbildenden Partikel erhalten bleibt.
- a) applying Fixiermittelpartikeln and structure-forming particles, on a surface, wherein first the Fixiermittelpartikel and then the structure-forming particles are applied to the surface, and
- b) melting the fixing agent particles for fixing the structure-forming particles and the fixing agent particles on the surface by brief heating, wherein the temperature at which the melting is carried out, and the duration of the melting are to be selected so that the fixing agent particles only partially fuse, wherein the Fixer particles at their points of contact stick together and the structure, in particular the structure in the nanometer range, the structure-forming particles is retained.
Es kann vorteilhaft sein, die Fixiermittelpartikel auf der Oberfläche vor dem Aufbringen der strukturbildenden Partikel anzuschmelzen, wobei unter Anschmelzen (oder auch Ansintern) das Zusammenkleben von Fixiermittelpartikeln an ihren Berührungspunkten zu verstehen ist.It may be advantageous to melt the fixing agent particles on the surface before the application of the structure-forming particles, wherein melting (or else sintering) is to be understood as meaning the sticking together of fixing agent particles at their points of contact.
Das Aufbringen der Partikel auf die Oberfläche kann auf eine dem Fachmann bekannte Weise z.B. durch Aufsprühen oder Aufpudern erfolgen. Die Oberfläche kann, je nach Verwendung des mit einer selbstreinigenden Oberfläche versehenen Gegenstandes, bereits Korrosionsschutz-, Farb- oder Warnbeschichtungen aufweisen.The particles may be applied to the surface in a manner known to those skilled in the art, for example by spraying or powdering. Depending on the use of the article provided with a self-cleaning surface, the surface may already have anticorrosive, color or warning coatings.
Das erfindungsgemäße Anschmelzen erfolgt durch kurzzeitiges Erwärmen, wobei unter Anschmelzen (oder auch Ansintern) ein Erweichen der Fixiermittelpartikel der Gestalt verstanden wird, dass die Oberfläche der Fixiermittelpartikel mit benachbarten Oberflächen von Fixiermittelpartikeln und/oder strukturbildenden Partikeln sowie der Oberfläche des Gegenstandes, welcher mit einer selbstreinigenden Oberfläche versehen wird, nach dem Erkalten zumindest teilweise aneinander haften. Die Haftung kann durch chemische Bindung aber auch durch physikalische Kräfte hergestellt worden sein.The melting according to the invention takes place by heating for a short time, melt melting (or else sintering) being understood to mean softening of the fixing agent particles such that the surface of the fixing agent particles has adjacent surfaces of fixing agent particles and / or structure-forming particles and of the surface of the object, which is self-cleaning Surface is provided, after cooling at least partially adhere to each other. The adhesion may have been produced by chemical bonding but also by physical forces.
Die Temperatur, bei der das Anschmelzen durchgeführt wird, sowie die Dauer des Anschmelzens sind so zu wählen, dass die Fixiermittelpartikel nur teilweise verschmelzen und die Struktur, insbesondere die Struktur im Nanometerbereich, der strukturbildenden Partikel erhalten bleibt.The temperature at which the melting is carried out, as well as the duration of the melting are to be chosen so that the fixer particles only partially melt and the structure, in particular the structure in the nanometer range, of the structure-forming particles is maintained.
Das Erwärmen kann auf eine dem Fachmann bekannte Weise, z.B. mittels eines Ofens oder einer anderen Wärmequelle erfolgen. Bevorzugt erfolgt das Erwärmen mittels Infrarotstrahlung. Es kann aber auch vorteilhaft sein, die Fixiermittelpartikel auf eine erwärmte Oberfläche aufzubringen, die nach dem Aufbringen abgekühlt wird. Dies kann insbesondere dann vorteilhaft sein, wenn die Oberfläche des Gegenstandes selbst der Gestalt ist, dass die aufgebrachten Fixiermittelpartikel nicht stabil auf dieser Oberfläche verbleibt. Gründe hierfür können z.B. auch in der Geometrie des Gegenstandes zu suchen sein, oder aber in einer ungenügenden Adhäsion der pulverförmigen Beschichtungsmittel (Fixiermittelpartikel oder strukturbildenden Partikel) zum Substrat.The heating may be carried out in a manner known to those skilled in the art, e.g. by means of a furnace or other heat source. Preferably, the heating takes place by means of infrared radiation. However, it can also be advantageous to apply the fixing agent particles to a heated surface, which is cooled after application. This may be advantageous, in particular, when the surface of the article itself is in the form that the applied fixing agent particles do not remain stable on this surface. Reasons for this may e.g. also be in the geometry of the article to be found, or in an insufficient adhesion of the powdery coating agent (Fixiermittelpartikel or structure-forming particles) to the substrate.
Durch leichtes Erwärmen können die strukturbildenden Partikel zumindest teilweise fest an die Fixiermittelpartikel gebunden werden, ohne dass ein Umschmelzen der strukturbildenden Partikel durch das Fixiermittel stattfindet, wodurch die Struktur der strukturbildenden Partikel im Nanometerbereich verlorengehen würde.By gentle heating, the structure-forming particles can at least partially be firmly bound to the fixing agent particles without the remelting of the structure-forming particles by the fixing agent taking place, as a result of which the structure of the structure-forming particles in the nanometer range would be lost.
Die erfindungsgemäß eingesetzten Fixiermittelpartikel weisen vorzugsweise eine durchschnittliche Größe von kleiner 50 µm auf. Bevorzugt weisen die Fixiermittelpartikel eine durchschnittliche Größe, die der Größe der strukturbildenden Partikel entspricht, auf. Es kann aber auch vorteilhaft sein, wenn die Fixiermittelpartikel eine von 10 bis 70 %, vorzugsweise 25 bis 50 % kleinere durchschnittliche Größe als die der strukturbildenden Partikel aufweisen.The fixing agent particles used according to the invention preferably have an average size of less than 50 μm. The fixer particles preferably have an average size which corresponds to the size of the structure-forming particles. However, it can also be advantageous if the fixing agent particles have a size which is smaller by 10 to 70%, preferably 25 to 50%, than that of the structure-forming particles.
Werden hydrophile strukturbildende Partikel mit hydrophilen Fixiermittelpartikeln zur Herstellung der selbstreinigenden Oberflächenstruktur eingesetzt, wird diese mit zumindest einer Verbindung aus der Gruppe der Alkylsilane, Alkyldisilazane, Wachse, Paraffine, Fettsäureester, fluorierte und/oder funktionalisierte Alkane oder Perfluoralkylsilane, behandelt um die selbstreinigende Oberfläche mit hydrophoben Eigenschaften auszustatten. Vorzugsweise erfolgt die Behandlung dadurch, dass die Partikel aufweisende Oberfläche, die hydrophobiert werden soll, in eine Lösung, die ein Hydrophobierungsreagenz wie z.B. Alkylsilane aufweist, getaucht wird, überschüssiges Hydrophobierungsreagenz abgetropft wird und die Oberfläche bei einer möglichst hohen Temperatur getempert. Die Behandlung kann aber auch durch Besprühen der Oberfläche mit einem ein Hydrophobierungsreagenz aufweisenden Medium und anschließende Temperung, erfolgen. Eine solche Behandlung ist z.B. für die Behandlung von Stahlträgern oder anderen schweren oder sperrigen Gegenständen bevorzugt. Die Begrenzung der Temperatur ist durch die Erweichungstemperaturen der Fixiermittel, der strukturbildenden Partikel und des Substrats, auf welches die selbstreinigende Oberfläche aufgebracht wurde, limitiert.If hydrophilic structure-forming particles with hydrophilic fixing agent particles are used to produce the self-cleaning surface structure, it is treated with at least one compound from the group of the alkylsilanes, alkyldisilazanes, waxes, paraffins, fatty acid esters, fluorinated and / or functionalized alkanes or perfluoroalkylsilanes, around the self-cleaning surface with hydrophobic Equip features. Preferably, the treatment is carried out by subjecting the particle-bearing surface to be hydrophobicized to a solution containing a hydrophobing reagent, such as e.g. Alkylsilane has, is dipped, excess hydrophobing reagent is drained and the surface is annealed at the highest possible temperature. The treatment can also be done by spraying the surface with a medium having a hydrophobizing reagent and subsequent heat treatment. Such a treatment is e.g. for the treatment of steel beams or other heavy or bulky objects. The limitation of the temperature is limited by the softening temperatures of the fixing agents, the structure-forming particles and the substrate to which the self-cleaning surface has been applied.
Das erfindungsgemäße Verfahren gemäß zumindest einem der Ansprüche 8 bis 15 kann hervorragend zur Herstellung von selbstreinigenden Oberflächen auf planaren oder nichtplanaren Gegenständen, insbesondere auf nichtplanaren Gegenständen verwendet werden. Dies ist mit den herkömmlichen Verfahren nur eingeschränkt möglich. Insbesondere über Verfahren, bei denen vorgefertigte Filme auf eine Oberfläche aufgebracht werden oder bei Verfahren, bei denen eine Struktur durch Prägen erstellt werden soll, sind nichtplanare Gegenstände, wie z.B. Skulpturen, nicht oder nur eingeschränkt zugänglich. Naturgemäße kann das erfindungsgemäße Verfahren aber auch zur Herstellung von selbstreinigenden Oberflächen auf Gegenständen mit planaren Oberflächen, wie z.B. Gewächshäusern oder öffentlichen Verkehrsmitteln verwendet werden. Insbesondere die Anwendung des erfindungsgemäßen Verfahrens zur Herstellung von selbstreinigenden Oberflächen an Gewächshäusern weist Vorteile auf, da mit dem Verfahren selbstreinigende Oberflächen z.B. auch auf transparenten Materialien wie Glas oder Plexiglas® hergestellt werden können und die selbstreinigende Oberfläche zumindest soweit transparent ausgebildet werden kann, dass für das Wachstum der Pflanzen im Gewächshaus genügend Sonnenlicht durch die mit einer selbstreinigenden Oberfläche ausgerüstete transparente Oberfläche dringen kann. Im Gegensatz zu herkömmlichen Gewächshäusern, die regelmäßig von Laub-, Staub-, Kalk- und biologischem Material, wie z.B. Algen, gereinigt werden müssen, können Gewächshäuser, die eine erfindungsgemäße Oberfläche gemäß einem der Ansprüche 1 bis 7, aufweisen, mit längeren Reinigungsintervallen betrieben werden.The process according to at least one of claims 8 to 15 can be used excellently for producing self-cleaning surfaces on planar or non-planar objects, in particular on non-planar objects. This is only possible to a limited extent with the conventional methods. In particular, by methods in which prefabricated films are applied to a surface or in processes in which a structure is to be created by embossing, non-planar objects, such as sculptures, are not or only partially accessible. Naturally, the inventive method but also for the production of self-cleaning surfaces can be used on objects with planar surfaces, such as greenhouses or public transport. In particular, the application of the method according to the invention for the production of self-cleaning surfaces on greenhouses has advantages, since with the method self-cleaning surfaces can be made, for example, on transparent materials such as glass or Plexiglas ® and the self-cleaning surface can be formed at least as far transparent that for the Growth of the plants in the greenhouse can penetrate enough sunlight through the provided with a self-cleaning surface transparent surface. In contrast to conventional greenhouses, which regularly have to be cleaned of deciduous, dust, lime and biological material, such as algae, greenhouses having a surface according to the invention according to one of claims 1 to 7, operated with longer cleaning intervals become.
Ebenso vorteilhaft kann das erfindungsgemäße Verfahren zur Ausrüstung von tragenden oder nicht tragenden Elementen des Hochbaus mit selbstreinigenden Oberflächen, ganz besonders dann, wenn ein Korrosionsschutz, eine Signalmarkierung, wie beispielsweise gelb-schwarzgestreifte Warntafeln oder eine Farbbeschichtung aufweist verwendet werden. Auf diese Weise kann erreicht werden, dass diese Elemente nicht dauerhaft verschmutzt werden, wodurch die Reinigungsintervalle vergrößert und signalisierende Farbgebungen ohne Beeinträchtigung durch Schmutz dauerhaft wahrnehmbar werden.Equally advantageously, the inventive method for finishing load-bearing or non-structural elements of building construction with self-cleaning surfaces, especially if a corrosion protection, a signal marking, such as yellow-black striped warning signs or a color coating having used. In this way it can be achieved that these elements are not permanently contaminated, whereby the cleaning intervals increases and signaling colorations are permanently noticeable without being affected by dirt.
Das erfindungsgemäße Verfahren kann außerdem zur Herstellung von selbstreinigenden Oberflächen auf nicht starren Oberflächen von Gegenständen, verwendet werden, wie z.B. Schirmen oder anderen Oberflächen, die flexibel gehalten sind. Ganz besonders bevorzugt kann das erfindungsgemäße Verfahren gemäß zumindest einem der Ansprüche 8 bis 15, zur Herstellung selbstreinigender Oberflächen auf flexiblen oder unflexiblen Wänden im Sanitärbereich verwendet werden. Solche Wände können z.B. Trennwände in öffentlichen Toiletten, Wände von Duschkabinen, Schwimmbädern oder Saunen, aber auch Duschvorhänge (flexible Wand) sein.The method of the invention may also be used to make self-cleaning surfaces on non-rigid surfaces of articles, such as e.g. Umbrellas or other surfaces that are kept flexible. With very particular preference, the process according to the invention according to at least one of claims 8 to 15 can be used for producing self-cleaning surfaces on flexible or inflexible walls in the sanitary sector. Such walls can e.g. Partitions in public toilets, walls of shower cubicles, swimming pools or saunas, but also shower curtains (flexible wall) be.
Die nachfolgenden Beispiele sollen die erfindungsgemäßen Oberflächen bzw. das Verfahren zur Herstellung der Oberflächen näher erläutern, ohne dass die Erfindung auf diese Ausführungsarten beschränkt sein soll.The following examples are intended to explain the surfaces according to the invention or the method for producing the surfaces, without the invention being restricted to these embodiments.
Auf eine 2 mm Dicke Platte aus Polymethylmethacrylat (PMMA) wird eine Mischung bestehend aus 50 Gew.-% Aeroperl 90/30 der Degussa AG, einer sprühgetrockneten pyrogenen Kieselsäure mit einer BET-Oberfläche von 90 m2/g, und 50 Gew.-% Polyamid-Schmelzkleber-Pulver (Vestamelt P06, Degussa AG) mit einer durchschnittlichen Teilchengröße unterhalb von <50 µm elektrostatisch aufgesprüht. Zur Fixierung der Partikel auf der Platte und Erzeugung einer zerklüfteten Struktur wird die Platte 5 min bei 108 °C getempert. Anschließend wird die Platte mit Antispread® (Dr. Tillwich GmbH), einem Oberflächenhydrophobierungsmittel, behandelt, wodurch die Hydrophobie der Partikel, bzw. der Oberfläche eingestellt wird. Die Charakterisierung der Oberfläche erfolgte anfänglich visuell und ist mit +++ protokolliert. +++ bedeutet, Wassertropfen bilden sich nahezu vollständig aus. Gemessen wurden Fortschreit- und Rückzugswinkel zu jeweils größer als 150°. Die zugehörige Hysterese liegt unterhalb von 10°.On a 2 mm thick plate of polymethyl methacrylate (PMMA) is a mixture consisting of 50 wt .-% Aeroperl 90/30 Degussa AG, a spray-dried fumed silica having a BET surface area of 90 m 2 / g, and 50 wt. % Polyamide hot-melt adhesive powder (Vestamelt P06, Degussa AG) with an average particle size below <50 microns sprayed electrostatically. To fix the particles on the plate and produce a fissured structure, the plate is annealed at 108 ° C for 5 min. Subsequently, the plate with Antispread ® (Dr. Tillwich GmbH), a surface hydrophobizing agent is treated so that the hydrophobicity of the particles, or the surface is adjusted. The characterization of the surface was initially visual and is logged with +++. +++ means, water droplets are almost completely formed. Progressive and retreatment angles greater than 150 ° each were measured. The associated hysteresis is below 10 °.
Ein Pulverlack (FREOPOX EKP-7, Emil Frei GmbH & Co.) wurde zu einer 200 µm dicken Schicht auf ein Nickelblech kalt aufgerakelt und mit einem hydrophoben Aerosil (R 8200, Degussa AG) bestreut. Diese Mischung und das Nickelblech wurden 3 Minuten einer Temperatur von 180 °C ausgesetzt. Nach dem Erkalten ließ sich nur eine geringfügige Verbesserung des Abperlverhaltens von Wasser beobachten.A powder coating (FREOPOX EKP-7, Emil Frei GmbH & Co.) was cold-doctored to a 200 μm thick layer on a nickel sheet and sprinkled with a hydrophobic Aerosil (R 8200, Degussa AG). This mixture and the nickel sheet were exposed to a temperature of 180 ° C for 3 minutes. After cooling, only a slight improvement in the bead behavior of water was observed.
Es wurde der Versuch aus Beispiel 1 wiederholt, jedoch wurde das Aerosil R 8200 mittels eines Metallrollers in den geschmolzenen Lack eingedrückt. Es wurde weitere 3 Minuten nachgetempert. Die erkaltete Platte zeigt nur einen geringfügig verbessertes Abperlverhalten gegenüber dem reinen Pulverlack.The experiment of Example 1 was repeated, but the Aerosil R 8200 was pressed by means of a metal roller into the molten paint. It was re-tempered for another 3 minutes. The cooled plate shows only a slightly improved Abperlverhalten compared to the pure powder coating.
Es wurde der Versuch aus Beispiel 1 wiederholt, jedoch wurde statt des Pulverlacks ein Schmelzkleber (Vestamelt P 06, Degussa AG) eingesetzt. Nach dem Erkalten ließ sich nur eine geringfügige Verbesserung des Abperlverhaltens von Wasser beobachten.The experiment of Example 1 was repeated, but instead of the powder coating a hot melt adhesive (Vestamelt P 06, Degussa AG) was used. After cooling, only a slight improvement in the bead behavior of water was observed.
Es wurde der Versuch aus Beispiel 1 wiederholt. Es wurde aber anstelle des hydrophoben Aerosils R 8200 eine hydrophile Kieselsäure (Sipernat 350, Degussa AG) eingesetzt. Nach dem Erkalten der Platte wurde mittels eines Hydrophobierungsreagenz (Antispread®, Dr. Tillwich GmbH) nachträglich hydrophobiert. Der Lotuseffekt war bei diesem Beispiel voll ausgeprägt.The experiment of Example 1 was repeated. However, instead of the hydrophobic Aerosils R 8200, a hydrophilic silica (Sipernat 350, Degussa AG) was used. After cooling, the plate by means of a hydrophobicizing reagent (Antispread ®, Dr. Tillwich GmbH) was rendered hydrophobic subsequently. The lotus effect was fully developed in this example.
Anhand der Beispiele 1 bis 4 lässt sich erkennen, dass eine Hydrophobiedifferenz von Fixiermittelpartikel (Pulverlack oder Schmelzkleber) zu strukturbildenden Partikel (Aerosil R8200) eine Anbindung des Strukturbilders an die Matrix verhindert. Bei der Verwendung einer hydrophileren Fällungskieselsäure (Sipernat 350) wird die Anbindung nicht verhindert und der Strukturbildner sintert fest mit den Lack- oder Kleberpartikeln aneinander.It can be seen from Examples 1 to 4 that a hydrophobicity difference of fixing agent particles (powder coating or hot melt adhesive) to structure-forming particles (Aerosil R8200) prevents binding of the structure image to the matrix. When using a more hydrophilic precipitated silica (Sipernat 350), the connection is not prevented and the structuring agent sinters firmly together with the paint or adhesive particles.
20 Gew.-% Methylmethacrylat, 20 Gew.-% Pentaeritrittetraacrylat und 60 Gew.-% Hexandioldimethacrylat wurden miteinander vermischt. Bezogen auf diese Mischung werden 14 Gew.-% Plex 4092 F, ein acrylisches Copolymerisat der Röhm GmbH und 2 Gew.-% UV-Härter Darokur 1173 zugesetzt und mindestens 60 min lang gerührt. Diese Mischung wurde als Träger auf eine 2 mm dicken PMMA-Platte in einer Dicke von 200 µm aufgetragen. Die Schicht wurde für 5 min angetrocknet. Auf diese angetrocknete Schicht wird eine Suspension von 10 Gew.-% sprühgetrocknete pyrogene Kieselsäure, Aeroperl 90/30 Degussa AG, eine Kieselsäure mit einer BET-Oberfläche von 90 m2/g, in Ethanol, aufgerakelt. Nach Härtung im UV-Licht und Behandlung mit dem Hydrophobierungsmittel Dynasilan 8262 wird die Oberfläche nur mit + beurteilt, d.h., der Tropfen bildet sich schlecht aus und klebt bis zu hohen Neigungswinkeln an der Oberfläche.20% by weight of methyl methacrylate, 20% by weight of pentaerythritol tetraacrylate and 60% by weight of hexanediol dimethacrylate were mixed together. Based on this mixture, 14% by weight Plex 4092 F, an acrylic copolymer from Röhm GmbH and 2% by weight Darokur 1173 UV curing agent are added and the mixture is stirred for at least 60 minutes. This mixture was applied as a support to a 2 mm thick PMMA plate in a thickness of 200 microns. The layer was dried for 5 minutes. A suspension of 10% by weight of spray-dried fumed silica, Aeroperl 90/30 Degussa AG, a silica having a BET surface area of 90 m 2 / g, in ethanol, is knife-coated onto this dried-on layer. After curing in UV light and treatment with the hydrophobing agent Dynasilan 8262, the surface is evaluated only with +, ie, the droplet forms poorly and sticks to high angles of inclination at the surface.
Der schlechte Lotuseffekt bei dem Vergleichsbeispiel ist auf Zuschmieren der zerklüfteten Struktur zurückzuführen. Dies geschieht durch Lösen von Monomeren in Ethanol. Vor dem Härten verdampft der Ethanol und der Härter bleibt bevorzugt in den zerklüfteten Strukturen zurück.The bad lotus effect in the comparative example is due to smearing of the fissured structure. This is done by dissolving monomers in ethanol. Before curing, the ethanol evaporates and the hardener preferably remains in the fissured structures.
Claims (19)
- Self-cleaning surface which has an artificial, at least to some extent hydrophobic, surface structure made from elevations and depressions,
characterized in that
the elevations and depressions are formed by- structure-forming particles secured to the surface, which have a fissured structure with elevations and/or depressions in the nanometer range and have hydrophobic properties, and by- the fixative particles used for the securing process are formed, which therefore likewise contribute to the formation of the elevations and depressions,where there is at least some mutual adhesion of the surfaces of the fixative particles to adjacent surfaces of fixative particles and/or structure-forming particles, so that the structure in the nanometer range of the structure-forming particles is retained. - Self-cleaning surface according to Claim 1,
characterized in that
the fixative particles encompass compounds selected from the group consisting of the hot-melt adhesives and/or powder coatings. - Self-cleaning surface according to Claim 2,
characterized in that
the hot-melt adhesives and/or powder coatings have been selected from the ethylene-ethyl acrylate copolymers, epoxy resins, ethylene-vinyl acetate copolymers, polyamides, polyether sulfones, polyisobutenes or polyvinyl butyrals. - Self-cleaning surface according to at least one of Claims 1 to 3,
characterized in that
the fixative particles have an average size of less than 50 µm. - Self-cleaning surface according to at least one of Claims 1 to 4,
characterized in that
the particles have an average size of less than 50 µm. - Self-cleaning surface according to Claim 5,
characterized in that
the particles have an average size of less than 30 µm. - Self-cleaning surface according to at least one of Claims 1 to 6,
characterized in that
the particles are composed of at least one material selected from silicates, doped silicates, minerals, metal oxides, silicas, polymers, and metal powders. - Process for producing self-cleaning surfaces according to at least one of Claims 1 to 7, which have an artificial, at least to some extent hydrophobic, surface structure made from elevations and depressions, where the elevations and depressions are formed by structure-forming particles secured to the surface,
characterized in that
the structure-forming particles, which have a fissured structure with elevations and/or depressions in the nanometer range and have hydrophobic properties are secured to the surface by using fixative particles which likewise contribute to formation of the elevations and depressions, and in that the process encompasses the following steps:a) applying fixative particles and structure-forming particles to a surface, first applying the fixative particles and then applying the structure-forming particles to the surface, andb) incipient melting of the fixative particles to secure the structure-forming particles and the fixative particles to the surface by brief heating, where the selection of the temperature at which the incipient melting is achieved and of the duration of the incipient melting is to be such that there is only partial melting of the fixative particles, whereupon the fixative particles agglutinate at their points of contact and the structure of the structure-forming particles, in particular the structure in the nanometer range, is retained. - Process according to Claim 8,
characterized in that
the application takes place by spray-application or powder-application. - Process according to Claim 8 or 9,
characterized in that
the heating takes place by means of infrared radiation. - Process according to Claim 8 or 10,
characterized in that
the structure-forming particles used comprise at least one material selected from silicates, doped silicates, minerals, metal oxides, silicas, metals, and polymers. - Process according to Claim 11,
characterized in that
the structure-forming particles used comprise particles whose average size is less than 50 µm. - Process according to at least one of Claims 8 to 12,
characterized in that
the fixative particles used comprise compounds selected from the group consisting of the hot-melt adhesives and/or powder coatings. - Process according to Claim 13,
characterized in that
the hot-melt adhesives and/or powder coatings encompass at least one compound selected from the ethylene-ethyl acrylate copolymers, ethylene-vinyl acetate copolymers, epoxy resins, polyamides, polyether sulfones, polyisobutenes, and polyvinyl butyrals. - Process according to at least one of Claims 8 to 14,
characterized in that
use is made of fixative particles which have an average size of less than 50 µm. - Use of the process according to at least one of Claims 8 to 15, for producing self-cleaning surfaces on planar or non-planar objects.
- Use of the process according to at least one of Claims 8 to 15, for producing self-cleaning surfaces on non-rigid surfaces of objects.
- Use of the process according to at least one of Claims 8 to 15, for producing self-cleaning surfaces on flexible or inflexible partitions in the sanitary sector.
- Use of the process according to at least one of Claims 8 to 15, for producing self-cleaning surfaces on corrosion-protected elements in buildings above ground level.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10118351 | 2001-04-12 | ||
DE10118351A DE10118351A1 (en) | 2001-04-12 | 2001-04-12 | Self-cleaning surfaces through hydrophobic structures and processes for their production |
Publications (2)
Publication Number | Publication Date |
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EP1249467A1 EP1249467A1 (en) | 2002-10-16 |
EP1249467B1 true EP1249467B1 (en) | 2007-09-12 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP02004728A Expired - Lifetime EP1249467B1 (en) | 2001-04-12 | 2002-03-01 | Self-cleaning surfaces due to hydrophobic structure and process for the preparation thereof |
Country Status (9)
Country | Link |
---|---|
US (1) | US6852389B2 (en) |
EP (1) | EP1249467B1 (en) |
JP (1) | JP2002347159A (en) |
AT (1) | ATE373039T1 (en) |
CA (1) | CA2381346A1 (en) |
DE (2) | DE10118351A1 (en) |
DK (1) | DK1249467T3 (en) |
ES (1) | ES2292653T3 (en) |
PT (1) | PT1249467E (en) |
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-
2001
- 2001-04-12 DE DE10118351A patent/DE10118351A1/en not_active Withdrawn
-
2002
- 2002-03-01 DE DE50210866T patent/DE50210866D1/en not_active Expired - Fee Related
- 2002-03-01 DK DK02004728T patent/DK1249467T3/en active
- 2002-03-01 PT PT02004728T patent/PT1249467E/en unknown
- 2002-03-01 EP EP02004728A patent/EP1249467B1/en not_active Expired - Lifetime
- 2002-03-01 ES ES02004728T patent/ES2292653T3/en not_active Expired - Lifetime
- 2002-03-01 AT AT02004728T patent/ATE373039T1/en not_active IP Right Cessation
- 2002-04-09 JP JP2002106943A patent/JP2002347159A/en not_active Ceased
- 2002-04-10 CA CA002381346A patent/CA2381346A1/en not_active Abandoned
- 2002-04-12 US US10/120,365 patent/US6852389B2/en not_active Expired - Fee Related
Also Published As
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US6852389B2 (en) | 2005-02-08 |
EP1249467A1 (en) | 2002-10-16 |
DE10118351A1 (en) | 2002-10-17 |
DK1249467T3 (en) | 2008-01-07 |
US20020150725A1 (en) | 2002-10-17 |
DE50210866D1 (en) | 2007-10-25 |
JP2002347159A (en) | 2002-12-04 |
PT1249467E (en) | 2007-11-23 |
CA2381346A1 (en) | 2002-10-12 |
ES2292653T3 (en) | 2008-03-16 |
ATE373039T1 (en) | 2007-09-15 |
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